CN102492064A - Preparation and application method of polyvinyl chloride (PVC) resin terminator - Google Patents
Preparation and application method of polyvinyl chloride (PVC) resin terminator Download PDFInfo
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Abstract
The invention relates to a preparation and application method of a polyvinyl chloride (PVC) resin terminator, belonging to the technical field of chemical products. The invention particularly relates to a liquid antioxidant product, which mainly comprises 2,6-di-bert-butyl-4-(1-phenylethyl)phenol and is obtained by carrying out catalytic alkylation reaction on 2,6-di-bert-butyl phenol and styrene as raw materials. An organic solvent is added into the liquid antioxidant product which mainly comprises the 2,6-di-bert-butyl-4-(1-phenylethyl)phenol, and is sufficiently stirred to obtain the liquid antioxidant product HKY-10. The HKY-10 is compounded with a benzofuran ketone antioxidant and a phosphite ester antioxidant to obtain an oil-soluble compound liquid terminator product as a terminator for a general-purpose PVC resin product preparation process by a suspension method; and the liquid terminator is added in a polymerization reaction process to obtain a PVC resin product with stable properties, thereby enhancing the aging whiteness of the PVC resin product. The PVC resin terminator has the characteristics of no toxicity and environmental protection, and does not generate water pollutants.
Description
Technical field
The present invention is a kind of preparation method of SE resin terminator, is used to improve the method for the universal SE of suspension method (PVC) rosin products stability.Be specifically related to by 2; 6-DI-tert-butylphenol compounds, vinylbenzene are raw material; Catalytic alkylation reaction prepares formula (
) and is the liquid antioxidant product of principal product; Both 2,6-di-t-butyl-4-(1-phenylethyl) phenol is the liquid antioxidant product of principal product; Relate to technical field of chemical products;
（
）
2,6-di-t-butyl-4-(1-phenylethyl) phenol is to add organic solvent in the liquid antioxidant product of principal product, fully stirs, and processes liquid antioxidant product HKY-10.
Background technology
By 2; 6-DI-tert-butylphenol compounds, vinylbenzene are raw material; Catalytic alkylation reaction prepares formula (
) and adds organic solvent in the liquid antioxidant product of principal product, fully stirs, and processes liquid antioxidant product HKY-10; A kind of benzofuranone kind antioxidant and a kind of phosphite ester kind antioxidant are compound; Process a kind of oil soluble, compound, liquid terminator product, prepare the terminator in the universal polyvinyl chloride resin product technological process, in polymerization process, add as suspension method; To obtain to have the polyvinyl chloride resin product of stability, improve ageing whiteness.Aqueous suspension polymerization is the main method of synthetic polyvinyl chloride resin, in water solution system, adds auxiliary agent and vinyl chloride monomer reaction raw materials such as dispersion agent, buffer reagent, initiator, pH value regulator, under the effect of stirring, makes the reactant high dispersing and becomes stable emulsion; Protective colloid in water is dispersed in vinyl chloride monomer in the small drop; Each drop is equivalent to a polymerization system, is dissolved in monomeric initiator and under polymerization temperature, resolves into radical, causes the polymerization of vinyl chloride monomer; Unit processes such as that whole polymerization process comprises is chain initiation, chainpropagation, chain termination; The SE that generates is insoluble in the monomer phase vinylchlorid, and initial reaction stage just is precipitated out mutually from vinyl chloride monomer, wads a quilt with cotton into primary particle with fixed attention; And finally grow into primary particle; Primary particle clinkering and assembling forms and has internal pore structure PVC particle, both polyvinyl chloride resin product.
Chain initiation is the reaction that monomer forms the free radical activity center, generally include decomposition of initiator and form elementary radical R,
Elementary radical and VCM addition form monomer radical CH
2Two steps of CHCI; The chainpropagation stage is on the basis of chain initiation formation monomer radical, and constantly the addition monomer molecule makes chainpropagation form macromole; Termination step comprises that radical interacts and stops, and the living chain radical of two growths interacts and makes chain termination, so the termination reaction of radical polymerization is dimolecular reaction, and two kinds of forms of coupling and disproportionation are arranged.Polymerization process later stage monomer concentration is lower, if rely on reaction to stop automatically, then stops occupying an leading position with the double-basis disproportionation, and two big PVC radical molecules meet and form a saturated macromole and stop; Another then is the unsaturated termination that has two keys, and the result causes small molecules quality PVC, the PVC that has side chain that is generated, the PVC product that has the chlorallylene structure to increase.Have the PVC thermostability extreme difference of this molecular structure, especially have chlorallylene on the molecular chain, have the height activity; Under the situation of being heated, be easy to dehydrochlorination, form the conjugated polyene structure, the HCl that the starting stage deviates from becomes PVC macromolecular chain continuation pyrolysated catalyzer again; Therefore, the reaction of dehydrochlorination Once you begin will make further reaction become more easy; Cause polyvinyl chloride resin product generation thermal ageing, yellow index increases whiteness and reduces.In addition under the effect of heat or light, the homolysis of C-Cl key takes place and generate high molecular free radical R, because the reaction activity of radical; Can carry out intermolecular or intramolecular further reaction stablizes obtaining; Under the situation that aerobic exists, be easy to take place the oxidizing reaction of radical especially, generate oxyradical RO, peroxylradicals ROO; Thereby further promoted the molecule crosslinked of SE, both caused the aging generation of SE.For this reason; Must, polyreaction begin to add terminator when arriving the terminal point of setting; The polyreaction terminal point approximately is chosen in during the transformation efficiency 70 ~ 85%, in order to improve the stability of PVC product, needs to eliminate radical and the residual initiators that remains in the resin; It also is the important evidence of design terminator compositing formula; The good termination agent can stop the reflex action of not expecting rapidly remaining initiator, elementary radical, monomer radical, the living chain radical termination of growth, inactivation in the still immediately, to obtain the good stable PVC molecular structure that has.Through polyvinyl chloride pulp centrifuged filtration; The oxidation inhibitor of various effects is dispersed in the PVC product of porous particle in the terminator; Continue that performance is caught the initiator activity group, caught oxyradical, the effect of peroxylradicals, hydroperoxide decomposition, make the polyvinyl chloride resin product in follow-up production technique with in storage, the use, have higher thermostability.
The terminator product needed is processed liquid dosage form, solution dosage or water miscible liquid formulation and just can be convenient to be dispersed in the PVC product of porous particle; Effectively bring into play the function of terminator; If the form with pressed powder adds, form the solid-liquid nonhomogeneous system, it is very low stopping usefulness.
The terminator that public reported is produced PVC has BHT, dihydroxyphenyl propane, antioxidant 1010,1076,2246,168 etc.; Phenolic antioxidant can make its inactivation with free radical reaction, because the thermolability that oxygen brought has obvious effects, resin thermo oxidative aging, raising ageing whiteness is also had certain effect for eliminating; But phenolic antioxidant can not with initiator for reaction; Remain in the inner initiator of resin particle and in follow-up operation, still can cause the accelerated deterioration of PVC product, efficient is very low under the one-component service condition usually, general large usage quantity; In addition; Use in BHT, dihydroxyphenyl propane, 1010,1076,2246,168 processes and will be dissolved into liquid dosage form with more a large amount of alcohol organic solvent, final alcohol organic solvent gets in the polyvinyl chloride pulp centrifuged mother liquor, and the COD of its waste discharge is obviously increased.Dihydroxyphenyl propane is the stronger phenols of toxicity, and certain solubility is arranged in water, and a part remains in the mother liquor and the polluted water environment in the use.
Acetone semicarbazone thiocarbamide (ATSC) is a kind of terminator of excellent property; Can be fast and radical and initiator for reaction; For eliminating polymerization later stage small molecules and branched chain molecule, and then the thermostability that improves product has certain effect, but not obvious to the effect of resin thermo oxidative aging.
The toxicity of dihydroxyphenyl propane, ATSC product and to be used for the negative impact that the PVC terminator brought be people's common recognition is because toxic effect has been limited use.
Chinese patent CN101735357A discloses a kind of method that improves ageing whiteness of vinyl chloride resin; Be that terminator, Tert. Butyl Hydroquinone are that the aqueous emulsion type oxidation inhibitor EB44-34 that anti-flake agent, Ciba company half hindered phenol antioxygen are processed is a chain terminator with the acetone semicarbazone thiocarbamide wherein, its weak point has been to use the bigger ATSC material of toxicity.
Chinese patent CN101921354A discloses the preparation method of the high PVC RESINS of a kind of transparency; Be single terminator wherein with acetone semicarbazone thiocarbamide or diethyl hydroxylamine; Or a kind of composite with in sulfo-propanedioic acid two lauryls and BHT, dihydroxyphenyl propane, the antioxidant 1076,1010; As terminator, its weak point has been to use the bigger ATSC material of toxicity; Or used BHT, the dihydroxyphenyl propane product that ecotope is had negative effect.
Chinese patent CN1657546A discloses the universal PVC RESINS preparation method of a kind of suspension method, is single terminator with the acetone semicarbazone thiocarbamide wherein, is mixed with 3 ~ 10% the aqueous solution during use, and its weak point has been to use the bigger ATSC material of toxicity.
Chinese patent CN1654486A discloses the multiplexing method that a kind of PVC RESINS prepares centrifugal slurry mother liquor in the process, is single terminator with acetone semicarbazone thiocarbamide or inhibitor wherein.
Chinese patent CN1649913A discloses a kind of PVC polymeric chain termination method, and wherein compound with dissociate nitroxyl and phenolic antioxidant is terminator,
In the method for the disclosed vinylchlorid aqueous suspension polymerization of Chinese patent CN1501945A, used nitroxide type stable free radical as polymerization terminator, or the mixture of nitroxide type stable free radical material and diethyl hydroxylamine is a terminator.
Terminator of the present invention is a kind of oil soluble, compound, liquid product; Prepare the terminator in the universal polyvinyl chloride resin product technological process as suspension method; Add during the terminal point that in polymerization process, sets; The living chain radical of residue initiator, elementary radical, monomer radical, growth in the still is stopped fast, inactivation; Avoid containing small molecules quality PVC in the finished product, have side chain PVC, have the PVC of chlorallylene structure, obtaining to have the polyvinyl chloride resin product of stability, from angle analysis, evaluation intuitively: the polyvinyl chloride resin product of acquisition has high whiteness and ageing whiteness.
Summary of the invention
The present invention is for overcoming above-mentioned deficiency of the prior art; A kind of oil soluble, compound, liquid terminator product have been invented; Prepare the terminator in the universal polyvinyl chloride resin product technological process as suspension method; In the polymerization process, select the vinyl chloride monomer transformation efficiency during 70 ~ 90%, to add, to obtain to have the polyvinyl chloride resin product of stability.
The compound liquid terminator of oil soluble product is made up of with a kind of benzofuranone kind antioxidant and a kind of phosphite ester kind antioxidant the HKY-10 of the present invention's preparation.
The preparation method of a kind of SE resin terminator according to the invention, carry out according to following step:
(1) preparation HKY-10: with 2,6 di t butyl phenol (being called for short 2,6-phenol) is raw material, and vinylbenzene is alkylating reagent; The employing organic acid compound is a catalyzer, adds a small amount of stopper, carries out catalytic alkylation reaction and generates with 2; 6-di-t-butyl-4-(1-phenylethyl) phenol is the liquid mixture of principal product, after reaction finishes, and cooling; In the adding and discoloring agent, organic solvent fully stirs; Process with 2,6-di-t-butyl-4-(1-phenylethyl) phenol is the liquid antioxidant product of principal product, i.e. HKY-10;
(2) HKY-10 is added in the reaction kettle with a kind of benzofuranone kind antioxidant and a kind of phosphite ester kind antioxidant in proportion successively, stir, be warming up to 50 ~ 80 ℃, fully stirred 30 ~ 60 minutes, process the compound liquid terminator of oil soluble product.
Organic acid catalyst described in the step (1) refers to: Witco 1298 Soft Acid, hexadecyl Phenylsulfonic acid, octadecyl Phenylsulfonic acid, two Witco 1298 Soft Acid, double hexadecyl Phenylsulfonic acid, two octadecyl Phenylsulfonic acid, decyl phenyl ether disulfonic acid, dodecyl phenyl ether disulfonic acid, hexadecyl phenyl ether disulfonic acid, two dodecyl phenyl ether disulfonic acid, double hexadecyl phenyl ether disulfonic acid, preferred Witco 1298 Soft Acid.
Stopper described in the step (1) refers to: 2, and 6-di-t-butyl-4-methylphenol; 2,2 '-ethylene two (4, the 6-di-tert-pentyl phenol); 2,2 '-ethylene two (4, the 6-DI-tert-butylphenol compounds); 2,2 '-methylene-bis (4, the 6-di-tert-pentyl phenol); 2,2 '-methylene-bis (4, the 6-DI-tert-butylphenol compounds); 2,2 '-methylene-bis(4-ethyl-6-t-butyl phenol); 2,2 '-methylene-bis (4-methyl-6-tert butyl phenol).β-(4-hydroxyl-3; The 5-di-tert-butyl-phenyl) the positive octadecyl ester of propionic acid, four (β-(3; The 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester, tricresyl phosphite (2; The 4-di-tert-butyl-phenyl) ester, phosphorous acid (three nonyl phenyl) ester, diphosphorous acid pentaerythritol stearic acid ester 2, two (2, the 4-di-tert-butyl-phenyl) pentaerythritol diphosphites, two (different tridecanol base) pentaerythritol diphosphites.
Refer to discoloring agent in described in the step (1): aminated compounds and Na
2CO
310H
2The mixture of O.Aminated compounds refers to: diethylamine; Triethylamine; Dipropyl amine; Tripropyl amine; Trioctylamine; Quadrol; 1, the 2-tn; N-hydroxyethyl-ethylenediamine; N, the N-dimethylethanolamine; N, the N-diethylethanolamine; Dimethyl hydroxylamine; Diethyl hydroxylamine; The N-isopropylhydroxyla; Diethylolamine; Trolamine; HSDB 338; A kind of in the tri-isopropanolamine.
Organic solvent described in the step (1) refers to: vinylbenzene; α-vinyl toluene; C
10~ C
16Straight-chain paraffin or isoparaffin.
System proportioning raw materials described in the step (1) is 2,6-phenol: vinylbenzene (mol ratio) is 1:0.60 ~ 2.0; Preferred suitable proportioning raw materials is 1:0.80 ~ 1.2.
The addition of catalyzer shows with 2 described in the step (1), 6-phenol: catalyzer (mass ratio) is 1:0.02 ~ 0.2, and preferred suitable mass ratio is 1:0.07 ~ 0.1.
The addition of the stopper described in the step (1) shows with 2,6-phenol: stopper (mass ratio) is 1:0.001-0.020; Selecting suitable mass ratio is 1:0.002-0.008.
Temperature of reaction described in the step (1) is 80-120 ℃; Under temperature of reaction, adopt vinylbenzene to drip feeding manner and 2 continuously, 6-phenol reacts, and it is 180 ~ 240 minutes that suitable vinylbenzene drips feed time; After charging was accomplished, under temperature of reaction, selecting the suitable insulation reaction time was 60 ~ 80 minutes.
The described cooling of step (1), selecting suitable cooling temperature is 60 ~ 80 ℃, in the adding and discoloring agent, and maintains and stirs under this temperature 20 ~ 30 minutes.
In described in the step (1) with the discoloring agent add-on by it with 2, the mass ratio meter of 6-phenol, 2,6-phenol: aminated compounds (mass ratio)=1:0.01 ~ 0.10, the mass ratio that suits is 1:0.05 ~ 0.10; In with discoloring agent in Na
2CO
310H
2The O add-on is the molar ratio computing of Witco 1298 Soft Acid by itself and organic acid catalyst, selects Na
2CO
310H
2O: Witco 1298 Soft Acid (mol ratio)=1:2.
Organic solvent add-on described in the step (1) is by itself and generation 2; 6-di-t-butyl-4-(1-phenylethyl) phenol is the mass ratio meter of the liquid mixture of principal product; Select suitable generation 2,6-di-t-butyl-4-(1-phenylethyl) phenol is the liquid mixture of principal product: organic solvent (mass ratio)=1:0.6 ~ 0.7.
Benzofuranone kind antioxidant described in the step (2) refers to: 5, and 7-di-t-butyl-3-(4-methyl) 3 hydrogen-benzofuran-2-ones; 5,7-di-t-butyl-3-(3, the 4-dimethyl-) 3 hydrogen-benzofuran-2-ones; 5,7-di-t-butyl-3-(2, the 4-dimethyl-) 3 hydrogen-benzofuran-2-ones or; 5,7-di-t-butyl-3-(2, the 3-dimethyl-) 3 hydrogen-benzofuran-2-ones;
Phosphite ester kind antioxidant described in the step (2) refers to the phosphite ester compound that has the Spirocyclic structure, and structural formula is following:
The phosphite ester kind antioxidant of Spirocyclic structure
As: two (different tridecanol base) pentaerythritol diphosphites; Two (phenylcarbinol base) pentaerythritol diphosphites; Two (lauryl alcohol base) pentaerythritol diphosphites; Two (hexadecanol base) pentaerythritol diphosphites; Two (stearyl alcohol base) pentaerythritol diphosphites.
Processing in the compound liquid terminator of the oil soluble product process described in the step (2); The cooperation ratio of three kinds of oxidation inhibitor is the benchmark metering with the organic solvent among the HKY-10; Wherein: the mass ratio of the organic solvent among the HKY-10 and a kind of benzofuranone kind antioxidant is 1:0.001 ~ 0.3, and suitable mass ratio is 1:0.08 ~ 0.10; Organic solvent among the HKY-10 and a kind of mass ratio of phosphite ester kind antioxidant are: 1:0.01 ~ 1.2, suitable mass ratio is 1:0.2 ~ 0.5.
The method of use of a kind of SE resin of the present invention terminator; Prepare in the universal polyvinyl chloride resin product technological process in known method; Select the vinyl chloride monomer transformation efficiency during 70 ~ 85%, to add terminator product of the present invention, add-on is pressed into 0. 05 ~ 0.08% of still vinyl chloride monomer massfraction.
Advantage of the present invention
1, the present invention selects by 2; 6-DI-tert-butylphenol compounds, vinylbenzene are raw material; Catalytic alkylation reaction prepares chemical structure shown in the formula (
); Both 2,6-di-t-butyl-4-(1-phenylethyl) oxybenzene compound, with benzofuranone kind antioxidant, phosphite ester kind antioxidant compound after; Very good with the polyvinyl chloride resin consistency; In the PVC of porous particle product, be uniformly dispersed, even under 160 ~ 200 ℃ of state of temperatures, terminator is difficult for constituting migration, volatilization loss.
2, the present invention is a raw material with HKY-10, benzofuranone kind antioxidant, phosphite ester kind antioxidant, processes a kind of oil soluble, compound, liquid terminator product, and this system has good synergistic, and it is high to stop efficient, and consumption is little; Terminator is dispersed in the polymerization liquid easily, and is easy to use.Add during the terminal point that in polymerization process, sets; The living chain radical of residue initiator, elementary radical, monomer radical, growth in the still is stopped fast, inactivation; Avoid containing small molecules quality PVC in the finished product, have side chain PVC, have the PVC of chlorallylene structure; To obtain to have the polyvinyl chloride resin product of stability, it has high whiteness and ageing whiteness.
3, the compound liquid terminator of oil soluble of the present invention has the advantages that production technique is simple, raw material is easy to get, the product use cost is low, be convenient to the industrialization promotion application.
4, the compound liquid terminator of oil soluble of the present invention has characteristic nontoxic, environmental protection, does not produce water pollutant.
Embodiment
The product that two (different tridecanol base) pentaerythritol diphosphites used in the present invention is Changzhou University's preparation, outward appearance is a colourless liquid; Other raw material, as: 2,6 di t butyl phenol, vinylbenzene, α-vinyl toluene, organic acid catalyst, stopper, in and discoloring agent, benzofuranone kind antioxidant, phosphite ester kind antioxidant be the commercially available prod, specification is industrial top grade article.
The method of use of a kind of SE resin of the present invention terminator; Prepare in the universal polyvinyl chloride resin product technological process with known method; Select the vinyl chloride monomer transformation efficiency during 70 ~ 85%, to add compound liquid terminator product of the present invention; To obtain to have the polyvinyl chloride resin product of stability, improve ageing whiteness.
Consider better to understand content of the present invention from following non-limiting example 1 ~ 4.
One,
The compound liquid terminator of oil soluble product prepn
Embodiment 1
In the 3000ml four-hole boiling flask that whisking appliance, TM, vinylbenzene tap funnel, reflux exchanger and nitrogen ingress pipe are housed, add the stopper of 750 gram 2,6 di t butyl phenols, 60 gram Witco 1298 Soft Acids, 2.5 grams, open and stir; Feed nitrogen and do nitrogen protection; Slowly be warming up to 110 ~ 112 ℃, under this temperature, begin drip styrene, the vinylbenzene feeding quantity is 455 grams; At the uniform velocity drip and in 195 ~ 200 minutes, accomplish, 110 ~ 112 ℃ of insulation reaction 60 minutes.Reaction finishes, and is cooled to 80 ℃, with discoloring agent diethyl hydroxylamine 46 grams, and maintains under this temperature and stirs 20 minutes in the adding, adds vinylbenzene 843 grams, stirs 30 minutes, and thorough mixing is processed HKY-10; Holding temperature adds benzofuranone kind antioxidant 68 grams, phosphite ester kind antioxidant 253 grams at 60 ~ 65 ℃, fully stirs 30 minutes, obtains the compound liquid terminator of 1# oil soluble product (1# terminator).
Embodiment 2
In the 3000ml four-hole boiling flask that whisking appliance, TM, vinylbenzene tap funnel, reflux exchanger and nitrogen ingress pipe are housed, add the stopper of 750 gram 2,6 di t butyl phenols, 53 gram Witco 1298 Soft Acids, 6.0 grams, open and stir; Feed nitrogen and do nitrogen protection; Slowly be warming up to 80 ~ 85 ℃, under this temperature, begin drip styrene, the vinylbenzene feeding quantity is 340 grams; At the uniform velocity drip and in 235 ~ 240 minutes, accomplish, 80 ~ 85 ℃ of insulation reaction 80 minutes.Reaction finishes, and is cooled to 60 ℃, with discoloring agent diethyl hydroxylamine 38 grams, and maintains under this temperature and stirs 20 minutes in the adding, adds Permethyl 99A. hydrocarbon 807 grams, stirs 30 minutes, and thorough mixing is processed HKY-10; Holding temperature adds benzofuranone kind antioxidant 60 grams, phosphite ester kind antioxidant 322 grams at 75 ~ 80 ℃, fully stirs 50 minutes, obtains the compound liquid terminator of 2# oil soluble product (2# terminator).
Embodiment 3
In the 3000ml four-hole boiling flask that whisking appliance, TM, vinylbenzene tap funnel, reflux exchanger and nitrogen ingress pipe are housed, add the stopper of 750 gram 2,6 di t butyl phenols, 67 gram Witco 1298 Soft Acids, 4.5 grams, open and stir; Feed nitrogen and do nitrogen protection; Slowly be warming up to 117 ~ 120 ℃, under this temperature, begin drip styrene, the vinylbenzene feeding quantity is 378 grams; At the uniform velocity drip and in 210 ~ 215 minutes, accomplish, 117 ~ 120 ℃ of insulation reaction 60 minutes.Reaction finishes, and is cooled to 70 ℃, with discoloring agent diethyl hydroxylamine 60 grams, and maintains under this temperature and stirs 30 minutes in the adding, adds α-vinyl toluene 800 grams, stirs 30 minutes, and thorough mixing is processed HKY-10; Holding temperature adds benzofuranone kind antioxidant 80 grams, phosphorous acid esters antioxygen 400 grams at 50 ~ 55 ℃, fully stirs 60 minutes, obtains the compound liquid terminator of 3# oil soluble product (3# terminator).
Embodiment 4
In the 3000ml four-hole boiling flask that whisking appliance, TM, vinylbenzene tap funnel, reflux exchanger and nitrogen ingress pipe are housed, add the stopper of 750 gram 2,6 di t butyl phenols, 75 gram Witco 1298 Soft Acids, 1.5 grams, open and stir; Feed nitrogen and do nitrogen protection; Slowly be warming up to 105 ~ 108 ℃, under this temperature, begin drip styrene, the vinylbenzene feeding quantity is 416 grams; At the uniform velocity drip and in 180 ~ 185 minutes, accomplish, 105 ~ 108 ℃ of insulation reaction 70 minutes.Reaction finishes, and is cooled to 80 ℃, with discoloring agent diethyl hydroxylamine 75 grams, and maintains under this temperature and stirs 20 minutes in the adding, adds vinylbenzene 878 grams, stirs 30 minutes, and thorough mixing is processed HKY-10; Holding temperature adds benzofuranone kind antioxidant 70 grams, phosphorous acid esters antioxygen 175 grams at 60 ~ 65 ℃, fully stirs 40 minutes, obtains the compound liquid terminator of 4# oil soluble product (4# terminator).
The comparative example 1
3% ATSC alkali aqueous solution had both contrasted the 1# terminator.
The comparative example 2
The mixture of 10% dihydroxyphenyl propane ethanolic soln had both contrasted the 2# terminator
Two,
Terminator product of the present invention is the effect evaluation experimental in the universal PVC RESINS of suspension method
Estimate the stabilization effect of the present invention's 1 ~ 4# terminator in the universal PVC RESINS of suspension method;
1, experimental raw
Still release agent (Italy is yellow, NOXOL WSW); Dispersion agent KH-20, L-10 (the synthetic Co., Ltd. of Japan), HPMC (The Dow Chemical Co. (US) 2030 Dow Center, Abbott Road, Midland, Michigan 48640); Initiator EHP is peroxy dicarbonate two (2-ethylhexyl) ester both), both peroxo-neodecanoic acid isopropyl benzene ester (Nobel Aksu, Tianjin ltd) of Tx99; The present invention 1 ~ 4# terminator; Other raw material, as: vinylchlorid; Bicarbonate of ammonia; The acetone semicarbazone thiocarbamide; Dihydroxyphenyl propane is the commercially available prod, and specification is industrial top grade article.
, the preparation sample (1 ~ 4# sample, control sample 1#)
In 10 liters of reactor drums of double-deck trilobed wheel type whisking appliance and double jacket are housed, carry out antiseized still in advance and handle, add 4350 gram deionized waters then; Bicarbonate of ammonia 0.47 gram; The KH-20 aqueous solution 2.8 grams of working substance content 20%, the L-10 aqueous solution 8.1 grams of working substance content 20%, the HPMC aqueous solution 20 grams of working substance content 1%; Active matter content is 40% EHP water miscible liquid 3.63 grams, and active matter content is 40% Tx99 water miscible liquid 1.09 grams.Being evacuated to the still pressure is-0.095MPa, after keep-uping pressure 5 minutes, adds vinylchlorid (VCM) monomer 3000 grams; With mixing speed 300rpm, stirred material in the thorough mixing still 15 minutes; Feed hot water to jacket of polymerization then, with 20 ~ 25 minutes, when making temperature in the kettle reach 57 ℃; Reacting kettle inner pressure is 0.83-0.88 MPa, and polymerization picks up counting.Polyreaction was carried out 15 minutes, in reaction kettle, added 1400 gram water with the at the uniform velocity amount of 400 Grams Per Hours, 0.1 ℃ of control still interior reaction temperature fluctuation range; The reaction carried out 5 ~ 5.5 hours, transformation efficiency be about 80%, begin to add terminator; Continue to stir 5 minutes at 56 ~ 58 ℃; Discharging, centrifuge dehydration, drying, sieve, obtain polyvinyl chloride resin sample and control sample, various terminators can be accomplished satisfied termination effect to polyreaction.
With aforesaid method, replacement is used the present invention's 1 ~ 4# terminator and is contrasted 1 ~ 2# terminator, processes 1# sample, 2# sample, 3# sample, 4# sample and control sample 1#, control sample 2# respectively.
, experimental technique
The employing standard, " GB/T 15595 PVC RESINS thermostability experimental technique whiteness methods "; " GB-T 2913-1982 plastics whiteness TP "; Measure whiteness and the ageing whiteness of 1 ~ 4# sample, control sample 1#, further specify the present invention.
, experimental result
The whiteness and the ageing whiteness of table 1,1 ~ 4# sample and control sample
Experimental result shows; Use ATSC, the terminator that dihydroxyphenyl propane is prepared of compound liquid terminator of oil soluble of the present invention and technology use in the past; Whiteness to prepared SE tree is variant, but ageing whiteness representes that apparently higher than the latter ageing resistance of terminator of the present invention is better than acetone semicarbazone thiocarbamide and dihydroxyphenyl propane; Prepare the terminator in the universal polyvinyl chloride resin product technological process with this as suspension method; In polymerization process, add, obtained to have the polyvinyl chloride resin product of stability, improved ageing whiteness.
Claims (10)
1. the preparation method of a SE resin terminator is characterized in that carrying out according to following step:
(1) preparation HKY-10: with the 2,6 di t butyl phenol is raw material, and vinylbenzene is alkylating reagent; The employing organic acid compound is a catalyzer, adds a small amount of stopper, carries out catalytic alkylation reaction and generates with 2; 6-di-t-butyl-4-(1-phenylethyl) phenol is the liquid mixture of principal product, after reaction finishes, and cooling; In the adding and discoloring agent, organic solvent fully stirs; Process with 2,6-di-t-butyl-4-(1-phenylethyl) phenol is the liquid antioxidant product of principal product, i.e. HKY-10;
(2) HKY-10 is added in the reaction kettle with a kind of benzofuranone kind antioxidant and a kind of phosphite ester kind antioxidant in proportion successively, stir, be warming up to 50 ~ 80 ℃, fully stirred 30 ~ 60 minutes, process the compound liquid terminator of oil soluble product.
2. the preparation method of a kind of SE resin terminator according to claim 1 is characterized in that the catalyzer described in the step (1) is Witco 1298 Soft Acid, hexadecyl Phenylsulfonic acid, octadecyl Phenylsulfonic acid, two Witco 1298 Soft Acid, double hexadecyl Phenylsulfonic acid, two octadecyl Phenylsulfonic acid, decyl phenyl ether disulfonic acid, dodecyl phenyl ether disulfonic acid, hexadecyl phenyl ether disulfonic acid, two dodecyl phenyl ether disulfonic acid or double hexadecyl phenyl ether disulfonic acid;
Stopper described in the step (1) is 2,6-di-t-butyl-4-methylphenol; 2,2 '-ethylene two (4, the 6-di-tert-pentyl phenol); 2,2 '-ethylene two (4, the 6-DI-tert-butylphenol compounds); 2,2 '-methylene-bis (4, the 6-di-tert-pentyl phenol); 2,2 '-methylene-bis (4, the 6-DI-tert-butylphenol compounds); 2,2 '-methylene-bis(4-ethyl-6-t-butyl phenol); 2,2 '-methylene-bis (4-methyl-6-tert butyl phenol);
β-(4-hydroxyl-3; The 5-di-tert-butyl-phenyl) the positive octadecyl ester of propionic acid, four (β-(3; The 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester, tricresyl phosphite (2; The 4-di-tert-butyl-phenyl) ester, phosphorous acid (three nonyl phenyl) ester, diphosphorous acid pentaerythritol stearic acid ester 2, two (2, the 4-di-tert-butyl-phenyl) pentaerythritol diphosphites or two (different tridecanol base) pentaerythritol diphosphites;
Refer to discoloring agent in described in the step (1): aminated compounds and Na
2CO
310H
2The mixture of O; Aminated compounds is a diethylamine; Triethylamine; Dipropyl amine; Tripropyl amine; Trioctylamine; Quadrol; 1, the 2-tn; N-hydroxyethyl-ethylenediamine; N, the N-dimethylethanolamine; N, the N-diethylethanolamine; Dimethyl hydroxylamine; Diethyl hydroxylamine; The N-isopropylhydroxyla; Diethylolamine; Trolamine; A kind of in HSDB 338 or the tri-isopropanolamine;
Organic solvent described in the step (1) is a vinylbenzene; α-vinyl toluene; C
10~ C
16Straight-chain paraffin or isoparaffin.
3. the preparation method of a kind of SE resin terminator according to claim 1 is characterized in that the system proportioning raw materials described in the step (1) is 2, and 6-phenol: cinnamic mol ratio is 1:0.60 ~ 2.0;
The addition of catalyzer shows with 2 described in the step (1), 6-phenol: the mass ratio of catalyzer is 1:0.02 ~ 0.2,
The addition of the stopper described in the step (1) shows with 2,6-phenol: the mass ratio of stopper is 1:0.001-0.020.
4. the preparation method of a kind of SE resin terminator according to claim 3 is characterized in that the system proportioning raw materials described in the step (1) is 2, and 6-phenol: cinnamic mol ratio is 1:0.80 ~ 1.2;
The addition of catalyzer shows with 2 described in the step (1), 6-phenol: the mass ratio of catalyzer is 1:0.07 ~ 0.1;
The addition of the stopper described in the step (1) shows with 2,6-phenol: the mass ratio of stopper is 1:0.002-0.008.
5. the preparation method of a kind of SE resin terminator according to claim 1 is characterized in that the temperature of reaction described in the step (1) is 80-120 ℃; Under temperature of reaction, adopt vinylbenzene to drip feeding manner and 2 continuously, 6-phenol reacts, and it is 180 ~ 240 minutes that vinylbenzene drips feed time; After charging was accomplished, under temperature of reaction, selecting the insulation reaction time was 60 ~ 80 minutes;
The described cooling of step (1), selecting the cooling temperature is 60 ~ 80 ℃, in the adding and discoloring agent, and maintains and stirs under this temperature 20 ~ 30 minutes;
In described in the step (1) with the discoloring agent add-on by itself and 2, the mass ratio meter of 6-phenol, 2,6-phenol: the mass ratio=1:0.01 of aminated compounds ~ 0.10; In with discoloring agent in Na
2CO
310H
2The O add-on is by itself and the molar ratio computing of organic acid catalyst, selection Na
2CO
310H
2O: the mol ratio=1:2 of Witco 1298 Soft Acid;
Organic solvent add-on described in the step (1) is by itself and generation 2; 6-di-t-butyl-4-(1-phenylethyl) phenol is the mass ratio meter of the liquid mixture of principal product; Select to generate 2,6-di-t-butyl-4-(1-phenylethyl) phenol is the liquid mixture of principal product: the mass ratio=1:0.6 of organic solvent ~ 0.7.
6. the preparation method of a kind of SE resin terminator according to claim 5; It is characterized in that described in the step (1) in the discoloring agent add-on by itself and 2; The mass ratio meter of 6-phenol, 2,6-phenol: the mass ratio of aminated compounds is 1:0.05 ~ 0.10.
7. the preparation method of a kind of SE resin terminator according to claim 1 is characterized in that the benzofuranone kind antioxidant described in the step (2) is 5,7-di-t-butyl-3-(4-methyl) 3 hydrogen-benzofuran-2-ones; 5,7-di-t-butyl-3-(3, the 4-dimethyl-) 3 hydrogen-benzofuran-2-ones; 5,7-di-t-butyl-3-(2, the 4-dimethyl-) 3 hydrogen-benzofuran-2-ones or 5,7-di-t-butyl-3-(2, the 3-dimethyl-) 3 hydrogen-benzofuran-2-ones;
Phosphite ester kind antioxidant described in the step (2) is the phosphite ester compound that has the Spirocyclic structure, and structural formula is following:
Processing in the compound liquid terminator of the oil soluble product process described in the step (2); The cooperation ratio of three kinds of oxidation inhibitor is the benchmark metering with the organic solvent among the HKY-10; Wherein: the mass ratio of the organic solvent among the HKY-10 and a kind of benzofuranone kind antioxidant is 1:0.001 ~ 0.3, and the organic solvent among the HKY-10 and a kind of mass ratio of phosphite ester kind antioxidant are: 1:0.01 ~ 1.2.
8. the preparation method of a kind of SE resin terminator according to claim 7 is characterized in that the phosphite ester kind antioxidant described in the step (2) is two (different tridecanol base) pentaerythritol diphosphites; Two (phenylcarbinol base) pentaerythritol diphosphites; Two (lauryl alcohol base) pentaerythritol diphosphites; Two (hexadecanol base) pentaerythritol diphosphites or two (stearyl alcohol base) pentaerythritol diphosphites.
9. the preparation method of a kind of SE resin terminator according to claim 7, it is characterized in that in the step (2) wherein: the mass ratio of the organic solvent among the HKY-10 and a kind of benzofuranone kind antioxidant is 1:0.08 ~ 0.10; Organic solvent among the HKY-10 and a kind of mass ratio of phosphite ester kind antioxidant are 1:0.2 ~ 0.5.
10. the method for use of a SE resin terminator; It is characterized in that preparing in the universal polyvinyl chloride resin product technological process in known method; Select the vinyl chloride monomer transformation efficiency during 70 ~ 85%, to add the terminator product, add-on is pressed into 0. 05 ~ 0.08% of still vinyl chloride monomer massfraction.
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| CN102786611A (en) * | 2012-07-30 | 2012-11-21 | 常州大学 | Organic alkali compound as pH value regulating agent for preparing polyvinyl chloride (PVC) resin |
| CN103012483A (en) * | 2012-12-04 | 2013-04-03 | 浙江海普顿新材料股份有限公司 | Phenol-free phosphite ester, as well as preparation method and application thereof |
| CN103288988A (en) * | 2013-06-19 | 2013-09-11 | 常州大学 | Preparation method of styrenated bisphenol A derivative for polyvinyl chloride terminating agent |
| CN103435725A (en) * | 2013-09-04 | 2013-12-11 | 武汉开元化学助剂有限公司 | Aqueous emulsion PVC (polyvinyl chloride) resin terminator and preparation method thereof |
| CN109575168A (en) * | 2018-12-10 | 2019-04-05 | 新沂市星辰新材料科技有限公司 | A kind of environment-friendly long-life PVC terminator and preparation method thereof |
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| CN102181000A (en) * | 2011-04-02 | 2011-09-14 | 西安道尔达化工有限公司 | Water-emulsion-type high-efficiency terminator for polyvinyl chloride and preparation method thereof |
| CN102199233A (en) * | 2011-03-31 | 2011-09-28 | 贵州大学 | Method for polymerizing polyvinyl chloride (PVC) resin by virtue of in-situ suspension |
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| US20050222347A1 (en) * | 2002-05-01 | 2005-10-06 | Rudolf Pfaendner | Process for chain stopping of pvc polymerization |
| CN102199233A (en) * | 2011-03-31 | 2011-09-28 | 贵州大学 | Method for polymerizing polyvinyl chloride (PVC) resin by virtue of in-situ suspension |
| CN102181000A (en) * | 2011-04-02 | 2011-09-14 | 西安道尔达化工有限公司 | Water-emulsion-type high-efficiency terminator for polyvinyl chloride and preparation method thereof |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102786611A (en) * | 2012-07-30 | 2012-11-21 | 常州大学 | Organic alkali compound as pH value regulating agent for preparing polyvinyl chloride (PVC) resin |
| CN103012483A (en) * | 2012-12-04 | 2013-04-03 | 浙江海普顿新材料股份有限公司 | Phenol-free phosphite ester, as well as preparation method and application thereof |
| CN103288988A (en) * | 2013-06-19 | 2013-09-11 | 常州大学 | Preparation method of styrenated bisphenol A derivative for polyvinyl chloride terminating agent |
| CN103288988B (en) * | 2013-06-19 | 2016-08-17 | 常州大学 | Styrol bisphenol-a derivative is as the preparation method of polrvinyl chloride terminator |
| CN103435725A (en) * | 2013-09-04 | 2013-12-11 | 武汉开元化学助剂有限公司 | Aqueous emulsion PVC (polyvinyl chloride) resin terminator and preparation method thereof |
| CN103435725B (en) * | 2013-09-04 | 2015-10-21 | 武汉开元化学助剂有限公司 | Aqueous emulsion type polyvinyl chloride (PVC) RESINS terminator and preparation method thereof |
| CN109575168A (en) * | 2018-12-10 | 2019-04-05 | 新沂市星辰新材料科技有限公司 | A kind of environment-friendly long-life PVC terminator and preparation method thereof |
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